Azonaphthalene sulfonates as polymerization catalysts

ABSTRACT

The present invention relates to a synthetic method comprising contacting at least one diaryl carbonate with one or more dihydroxy aromatic compounds in the presence of a transesterification catalyst under melt polymerization conditions to afford a product polycarbonate. The transesterifcation catalysts used according to the method of the present invention are azonaphthalene sulfonates in combination with tetraalkylammonium or tetraalkylphosphonium compounds which serve as co-catalysts. The transesterification catalysts employed according to the method of the present invention provide polycarbonates having reduced levels of Fries rearrangement product relative to conventionally employed catalysts such as sodium hydroxide in combination with tetramethylammonium hydroxide co-catalyst.

BACKGROUND OF THE INVENTION

This invention relates to azonaphthalene sulfonates useful astransesterification catalysts in melt polymerization reactions ofdihydroxy aromatic compounds with diaryl carbonates. Suitableazonaphthalene sulfonates are those that comprise alkali metalcounterions. The invention further relates to a method for thepreparation of polycarbonates using these azonaphthalene sulfonates. Themethod provides a product polycarbonate comprising a lower level of Fresproduct than is provided by other known methods employing conventionalmelt transestenfication catalysts.

Increasingly, polycarbonate is being prepared by the melt reaction of adiaryl carbonate with a dihydroxy aromatic compound in the presence of atransesterification catalyst, such as sodium hydroxide. In this “melt”process, reactants are introduced into a reactor capable of stirring aviscous polycarbonate melt at temperatures in excess of 300° C.Typically, the reaction is run at reduced pressure to facilitate theremoval of by-product hydroxy aromatic compound formed as the diarylcarbonate reacts with the dihydroxy aromatic compound and growingpolymer chains.

The Fries rearrangement is a ubiquitous side reaction taking placeduring the preparation of polycarbonate using the melt process. Theresultant “Fries product” serves as a site for branching of thepolycarbonate chains thereby affecting flow and other properties of thepolycarbonate. Although, a low level of Fries product may be toleratedin the product polycarbonate produced by the melt process, the presenceof higher levels of Fries product may negatively impact performancecharacteristics of the polycarbonate, such as moldability and toughness.Currently, alkali metal hydroxides, such as sodium hydroxide, areemployed as catalysts in the preparation of polycarbonate using the meltprocess. Alkali metal hydroxides, although effective catalysts in termsof rates of conversion of starting materials to product polycarbonate,tend to produce relatively high levels of Fries rearrangement product.Thus, melt polymerization methodology useful for the preparation ofpolycarbonate in which the formation of Fries product has been minimizedrepresents a long sought goal among those wishing to practice suchmethodology.

It would be a significant advantage to prepare polycarbonate by a meltpolymerization method that provides high rates of polymerization whileminimizing the amount of Fries product formation.

BRIEF SUMMARY OF THE INVENTION

The present invention provides a method for the preparation ofpolycarbonate, said method comprising contacting under meltpolymerization conditions at least one diaryl carbonate with at leastone dihydroxy aromatic compound in the presence of a transesterificationcatalyst to afford a polycarbonate, said transesterification catalystcomprising at least one azonaphthalene sulfonate catalyst and at leastone co-catalyst.

In one aspect the method of the present invention affords a productpolycarbonate having a lower level of Fries rearrangement product thanpolycarbonate prepared using a conventional melt transesterificationcatalyst.

The present invention further relates to a method of preparingpolycarbonate by the melt reaction of at least one dihydroxy aromaticcompound with at least one diaryl carbonate in the presence of at leastone transesterification catalyst comprising an azonaphthalene sulfonate.Azonaphthalene sulfonates are a well-known class of dyestuffs, whosecatalytic properties in the melt polycarbonate arena remainedundiscovered until the present invention. In its broadest sense, theterm azonaphthalene sulfonate includes organic molecules comprising thefollowing elements; an azo group (—N═N—), a naphthalene ring, and asulfonate group (SO₃Y⁺) wherein Y⁺ is a charge-balancing counterion. Inone embodiment of the present invention the azonaphthalene catalyst hasstructure I

wherein Ar₁ is a C₄-C₆₀ aromatic radical having a valence of at leastone, said aromatic radical being optionally substituted by one or morehydroxy groups, amino groups, C₁-C₁₀ alkylamino groups, C₂-C₂₀dialkylamino groups, C₁-C₂₀ aliphatic radicals, C₄-C₂₀ cycloaliphaticradicals, C₄-C₁₀ aromatic radicals, C₁-C₁₀ alkoxy groups, halogen atoms,and alkali metal sulfonate groups;

M is independently at each occurrence a lithium, sodium, potassium, orcesium ion;

n and m are integers independently having values of from 0 to 2 whereinthe sum of n and m is always greater than or equal to 1;

R₁ is independently at each occurrence a hydroxy group, amino group,C₁-C₁₀ alkylamino group, C₂-C₂₀ dialkylamino group, C₁-C₂₀ aliphaticradical, C₄-C₂₀ cycloaliphatic radical, C₄-C₁₀ aromatic radical, C₁-C₁₀alkoxy group, halogen atom, nitro group, or a cyano group;

q is an integer having a value of from 0 to 3;

p is an integer having a value of from 0-4; and

r is an integer having a value of from 1-4.

DETAILED DESCRIPTION OF THE INVENTION

The present invention may be understood more readily by reference to thefollowing detailed description of preferred embodiments of the inventionand the examples included therein. In the following specification andthe claims which follow, reference will be made to a number of termswhich shall be defined to have the following meanings:

The singular forms “a”, “an” and “the” include plural referents unlessthe context clearly dictates otherwise.

“Optional” or “optionally” means that the subsequently described eventor circumstance may or may not occur, and that the description includesinstances where the event occurs and instances where it does not.

As used herein the term “polycarbonate” refers to polycarbonatesincorporating structural units derived from at least one dihydroxyaromatic compound and includes copolycarbonates and polyestercarbonates.

As used herein, the term “melt polycarbonate” refers to a polycarbonatemade by a process comprising the transesterification of a diarylcarbonate with a dihydroxy aromatic compound in the presence of atransesterification catalyst.

“BPA” is herein defined as bisphenol A or2,2-bis(4-hydroxyphenyl)propane.

As used herein when describing the instant invention, the term“transesterification catalyst” refers to a catalyst system comprising atleast one “principal catalyst” and at least one co-catalyst. ForExample, in one embodiment of the instant invention diphenyl carbonateand bisphenol A are melt polymerized in the presence of atransesterification catalyst comprising an azonaphthalene sulfonate andtetramethylammonium hydroxide, the azonaphthalene sulfonate being theprincipal catalyst and tetramethylammonium hydroxide being theco-catalyst.

“Catalyst system” as used herein refers to the catalyst or catalyststhat catalyze the transesterification of the dihydroxy aromatic compoundwith the diaryl carbonate in the preparation of melt polycarbonate.

“Catalytically effective amount” refers to the amount of the catalyst atwhich catalytic performance is exhibited.

As used herein the term “Fries product” is defined as a structural unitof the product polycarbonate which upon hydrolysis of the productpolycarbonate affords a carboxy-substituted dihydroxy aromatic compoundbearing a carboxy group adjacent to one or both of the hydroxy groups ofsaid carboxy-substituted dihydroxy aromatic compound. For example, inbisphenol A polycarbonate prepared by a melt reaction method in whichFries reaction occurs, the Fries product affords carboxy bisphenol A,II, upon complete hydrolysis of the product polycarbonate.

The terms “Fries product” and “Fries group” are used interchangeablyherein.

The terms “Fries reaction” and “Fries rearrangement” are usedinterchangeably herein.

As used herein the term “hydroxy aromatic compound” means a phenol, suchas phenol, p-cresol or methyl salicylate, comprising a single reactivehydroxy group and is used interchangeably with the term “phenolicby-product”.

As used herein the term “aromatic radical” refers to a radical having avalence of at least one and comprising at least one aromatic ring.Examples of aromatic radicals include phenyl, pyridyl, furanyl, thienyl,naphthyl, phenylene, and biphenyl. The term includes groups containingboth aromatic and aliphatic components, for example a benzyl group, aphenethyl group or a naphthylmethyl group. The term also includes groupscomprising both aromatic and cycloaliphatic groups for example4-cyclopropylphenyl and 1,2,3,4-tetrahydronaphthalen-1-yl.

As used herein the term “aliphatic radical” refers to a radical having avalence of at least one and consisting of a linear or branched array ofatoms which is not cyclic. The array may include heteroatoms such asnitrogen, sulfur and oxygen or may be composed exclusively of carbon andhydrogen. Examples of aliphatic radicals include methyl, methylene,ethyl, ethylene, hexyl, hexamethylene and the like.

As used herein the term “cycloaliphatic radical” refers to a radicalhaving a valance of at least one and comprising an array of atoms whichis cyclic but which is not aromatic, and which does not further comprisean aromatic ring. The array may include heteroatoms such as nitrogen,sulfur and oxygen or may be composed exclusively of carbon and hydrogen.Examples of cycloaliphatic radicals include cyclopropyl, cyclopentylcyclohexyl, 2-cyclohexylethy-1-yl, tetrahydrofuranyl and the like.

It should be understood that as used herein, the terms “aliphaticradical”, “aromatic radical” and “cycloaliphatic radical” include bothsubstituted and unsubstituted embodiments of said radicals. For example,a radical comprising the cyclohexane ring structure alone may beregarded as an unsubstituted cycloaliphatic radical and an analogous sixmembered ring structure comprising a methyl group (CH₃) may be taken asan example of a substituted cycloaliphatic radical. Typical substituentsaccording to the present invention for the substituted forms ofaliphatic, aromatic, and cycloaliphatic radicals, include C₁-C₂₀ alkyl,C₃-C₂₀ cycloalkyl, C₄-C₂₀ aryl, halogen, hydroxy, carbonyl, nitro,cyano, C₁-C₂₀ alkoxy, C₁-C₂₀ alkoxycarbonyl, and the like.

It should be understood that the terms “mmHg” and “torr” are usedinterchangeably herein as units of pressure.

It has been discovered that the use of transesterification catalystscomprising azonaphthalene sulfonates as the principal catalyst in themelt transesterification reaction of a dihydroxy aromatic compound suchas bisphenol A with a diaryl carbonate such as diphenyl carbonate,provides a product polycarbonate having a reduced level of Friesrearrangement product relative to polycarbonates prepared with aconventional transesterification catalyst comprising sodium hydroxide asthe principal catalyst. This reduction in the amount of Friesrearrangement is highly desirable in that it results in increasedductility of the product polycarbonate and avoids uncontrolled branchingthat may occur at sites of Fries rearrangement. Uncontrolled branchingmay limit the utility of the product polycarbonate by reducing theductility of the product polycarbonate. Transesterification catalystscomprising azonaphthalene sulfonates used according to the method of thepresent invention, produced less Fries rearrangement product than didtransesterification catalysts comprising alkali metal hydroxides, suchas sodium hydroxide.

In one embodiment, the present invention provides a transesterificationcatalyst comprising at least one azonaphthalene sulfonate as theprincipal catalyst for the production of polycarbonate under meltpolymerization conditions wherein the polycarbonate has a number averagemolecular weight, M_(n) of at least about 7000 daltons and a reducedcontent of Fries products relative to a polycarbonate of comparablemolecular weight prepared using a transesterification catalystcomprising an alkali metal hydroxide as the principal catalyst. Inparticular, it is desirable to have Fries product of less than 3000 ppm,preferably less than 2000 ppm, more preferably less than 1000 ppm, evenmore preferably less than 500 ppm.

The present invention relates to azonaphthalene sulfonates useful ascatalysts in the melt polymerization of dihydroxy aromatic compoundswith diaryl carbonates. Azonaphthalene sulfonates having structure I areeffective melt polymerization catalysts and are exemplified byazonaphthalene sulfonates III, IV and V.

Catalysts having general structure I ate commercially available or maybe prepared by known methods, for example as described in Kirk-OthmerEncyclopedia of Chemical Technology, Fourth Edition, Volume 8, page 542,and Tetrahedron Letters pages 1941-6 (1968).

Dihydroxy aromatic compounds which are useful in preparingpolycarbonates according to the method of the present invention may berepresented by the general formula VI

wherein R² is independently at each occurrence a halogen atom, nitrogroup, cyano group, C₁-C₂₀ alkyl group, C₄-C₂₀ cycloalkyl group, orC₆-C₂₀ aryl group; b and c are independently integers 0-3; and W is abond, an oxygen atom, a sulfur atom, a SO₂ group, a C₁-C₂₀ aliphaticradical, a C₆-C₂₀ aromatic radical, a C₆-C₂₀ cycloaliphatic radical orthe group

wherein R³ and R⁴ are independently a hydrogen atom, C₁-C₂₀ alkyl group,C₄-C₂₀ cycloalkyl group, or C₄-C₂₀ aryl group; or R³ and R⁴ togetherform a C₄-C₂₀ cycloaliphatic ring which is optionally substituted by oneor more C₁-C₂₀ alkyl, C₆-C₂₀ aryl, C₅-C₂₁ aralkyl, C₅-C₂₀ cycloalkylgroups or a combination thereof.

Suitable bisphenols VI according to the method of the present inventioninclude bisphenol A; 2,2-bis(4-hydroxy-3-methylphenyl)propane;2,2-bis(3-chloro-4-hydroxyphenyl)propane;2,2-bis(3-bromo-4-hydroxyphenyl)propane;2,2-bis(4-hydroxy-3-isopropylphenyl)propane;1,1-bis(4-hydroxyphenyl)cyclohexane;1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane; and1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

In one aspect of the present invention, the diaryl carbonate usedaccording to the method of the present invention has structure VII

wherein R⁵ is independently at each occurrence a halogen atom, nitrogroup, cyano group, C₁-C₂₀ alkyl group, C₁-C₂₀ alkoxycarbonyl group,C₄-C₂₀ cycloalkyl group, or C₆-C₂₀ aryl group; and t and v areindependently integers 0-5.

Diaryl carbonates VI suitable for use according to the method of thepresent invention are illustrated by diphenyl carbonate,bis(4-methylphenyl) carbonate, bis(4-chlorophenyl) carbonate,bis(4-fluorophenyl) carbonate, bis(2-chlorophenyl) carbonate,bis(2,4-difluorophenyl) carbonate, bis(4-nitrophenyl) carbonate,bis(2-nitrophenyl) carbonate, and bis(methyl salicyl) carbonate (CAS No.82091-12-1).

In one embodiment, structural units of the product polycarbonate derivedfrom the dihydroxy aromatic compound are comprised entirely ofstructural units derived from bisphenol A, and structural units derivedfrom the diaryl carbonate are derived entirely from diphenyl carbonate.

Optionally, one or more branching agents may be included during the meltpolymerization reaction according to the method of the present inventionas a means of effecting the controlled branching of the productpolycarbonate as is sometimes desirable in applications, such as in blowmolding of beverage bottles, requiring a high degree level of meltstrength. Suitable branching agents include1,1,1-tris(4-hydroxyphenyl)ethane (THPE) and 1,3,5-trihydroxybenzene.

In the process of the present invention, an endcapping agent mayoptionally be used. Suitable endcapping agents include hydroxy aromaticcompounds such as phenol, p-tert-butylphenol, p-cumylphenol, cardanoland the like.

When an endcapping agent is employed said endcapping agent is preferablyused in an amount corresponding to between about 0.001 and about 0.10moles, preferably about 0.01 to about 0.08 moles per mole of thedihydroxy aromatic compound employed.

The azonaphthalene sulfonate catalyst having structure I is employed inan amount corresponding to between about 1×10⁻⁸ and 2.5×10⁻⁴, preferablybetween about 1×10⁻⁷ and 2.5×10⁻⁵ moles of catalyst per mole ofdihydroxy aromatic compound employed. When the amount of catalystemployed is less than 1×10⁻⁸ mole of catalyst per mole of dihydroxyaromatic compound employed, reaction rates may be reduced to such anextent that no appreciable molecular weight gain is observed. Generally,it is preferred that the number average molecular weight (M_(n)) of theproduct polycarbonate be at least about 7000 daltons. When the amount ofcatalyst is in excess of about 2.5×10⁻⁴ moles per mole of dihydroxyaromatic compound employed, rates of Fries rearrangement may beexcessive and high levels of uncontrolled branching may occur.

The co-catalyst used according to the method of the present invention isa quaternary ammonium compound, a quaternary phosphonium compound, or amixture thereof.

Examples of suitable quaternary ammonium compounds include, but are notlimited to ammonium hydroxides having alkyl groups, aryl groups andalkaryl groups, such as tetramethylammonium hydroxide (TMAH) andtetrabutylammonium hydroxide (TBAH). Suitable phosphonium compoundsinclude, but are not limited to tetraethylphosphonium hydroxide,tetrabutylphosphonium hydroxide, and tetrabutylphosphonium acetate.

The co-catalyst is preferably used in amounts of from about 1×10⁻² toabout 1×10⁻⁶, preferably about 1×10⁻² to about 1×10⁻⁵ moles per mole ofdihydroxy aromatic compound.

In some instances the reaction mixture may further comprise a metalhydroxide, for example, an alkali metal hydroxide such as sodiumhydroxide. The alkali metal hydroxide may be added to enhance theactivity of the azonaphthalene sulfonate principal catalyst. If present,the alkali metal hydroxide is preferably present in an amountcorresponding to between about 1×10⁻⁸ and 2.5×10⁻⁴ preferably 1×10⁻⁷ to1×10⁻⁵ moles of alkali metal hydroxide per mole of dihydroxy aromaticcompound employed.

The reaction conditions of the melt polymerization are not particularlylimited and may be conducted under a wide range of operating conditions.Hence, the term “melt polymerization conditions” will be understood tomean those conditions necessary to effect reaction between the diarylcarbonate and the dihydroxy aromatic compound of the present invention.The reaction temperature is typically in the range of about 100° C. toabout 350° C., more preferably about 180° C. to about 310° C. Thepressure may be at atmospheric pressure, supraatmospheric pressure, or arange of pressures from atmospheric pressure to about 15 torr in theinitial stages of the reaction, and at a reduced pressure at laterstages, for example in the range of about 0.2 to about 15 torr. Thereaction time is generally about 0.1 hours to about 10 hours.

The melt polymerization may be accomplished in one or more stages, as isknown in the art with other catalysts. The principal catalyst andco-catalysts of the present invention may be added in the same stage ordifferent stages, if the melt polymerization is conducted in more thanone stage. The co-catalyst may be added at any stage, although it ispreferred that it be added early in the process. The co-catalyst ispreferably utilized in an amount corresponding to between about 1 andabout 500 molar equivalents, based on the moles of primary catalyst Iutilized.

In a further preferred embodiment, the process is conducted as a twostage process. In the first stage of this embodiment, the co-catalyst isintroduced into the reaction system comprising the dihydroxy aromaticcompound and the diaryl carbonate. The first stage is conducted at atemperature of 270° C. or lower, preferably 80° C. to 250° C., morepreferably 100° C. to 230° C. The duration of the first stage ispreferably 0.1 to 5 hours, even more preferably 0.1 to 3 hours at apressure from about atmospheric pressure to about 100 torr, with anitrogen atmosphere preferred.

In a second stage, the catalyst having structure I is introduced intothe product from the first stage and further polycondensation isconducted. The catalyst may be added in its entire amount in the secondstage, or it may be added in batches in the second and any subsequentstages so that the total amount is within the aforementioned ranges.

It is preferable in the second and any subsequent stages of thepolycondensation step for the reaction temperature to be raised whilethe reaction system is reduced in pressure compared to the first stage,thus bringing about a reaction between the dihydroxy aromatic compoundand the diaryl carbonate. Thus there is formed initially a polycarbonateoligomer which upon further polycondensation reaction at 240° C. to 320°C. under reduced pressure of 5 mm Hg or less, and preferably 1 mm Hg orless, affords polycarbonate having a number average molecular weight ofabout 7000 daltons or greater.

If the melt polymerization is conducted in more than one stage, as notedabove, it is preferable to add the cocatalyst, for example,tetramethylammonium hydroxide, tetrabutylammonium hydroxide,tetrabutylphosphonium hydroxide, or tetrabutylphosphonium acetate, in anearlier stage than the principal catalyst of the present invention. Inparticular, it is preferable to add the co-catalyst to the reactorbefore the temperature reaches 220° C., preferably before it reaches200° C.

The reaction can be conducted as a batch or a continuous process. Anydesired apparatus can be used for the reaction. The material and thestructure of the reactor used in the present invention is notparticularly limited as long as the reactor has an ordinary capabilityof stirring and is equipped for the removal of by-product hydroxyaromatic compound formed during the course of the polymerization. It ispreferable that the reactor is capable of stirring in high viscosityconditions as the viscosity of the reaction system is increased in laterstages of the reaction.

Thus, in a further embodiment, the present invention provides a methodfor preparing polycarbonates, which comprises the steps of

(a) heating a dihydroxy aromatic compound and a-diaryl carbonate for atime period sufficient to form a melt, and thereafter introducing acatalyst composition comprising a catalytically effective amount of anazonaphthalene sulfonate compound having structure I and a co-catalystselected from tetraalkylammonium and tetraalkylphosphonium compounds;

(b) oligomerizing the melt mixture formed in step (a) in a reactionsystem comprising at least one continuous reactor in series, whereinsaid reactor is operated at a temperature of about 210° C. to about 290°C., and wherein the product from the reactor has a number averagemolecular weight of from about 1000 to about 5500 daltons; and

(c) polymerizing the product from step (b) in a reaction systemcomprising at least one continuous polymerization reactor in series,wherein said reactor is operated at a temperature of about 280° C. to315° C., wherein the product from step (c) has a number averagemolecular weight of at least about 7000 daltons.

Additives may also be added to the polycarbonate product as long as theydo not adversely affect the properties of the product. These additivesinclude a wide range of substances that are conventionally added to thepolycarbonates for a variety of purposes. Specific examples include heatstabilizers, epoxy compounds, ultraviolet absorbers, mold releaseagents, colorants, antistatic agents, slipping agents, anti-blockingagents, lubricants, antifogging agents, natural oils, synthetic oils,waxes, organic fillers, flame retardants, inorganic fillers and anyother commonly known class of additives.

The polycarbonate obtained in accordance with the present invention maybe used after being mixed with conventional additives, such asplasticizers, pigments, lubricants, mold release agents, stabilizers andorganic fillers. It is also possible to blend the polycarbonate withother polymers, including but not limited to, olefin polymers such asABS and polystyrenes, polyesters, polyacrylates, polyethersulfones,polyamides, and polyphenylene ethers.

EXAMPLES

The following examples are set forth to provide those of ordinary skillin the art with a detailed description of how the methods claimed hereinare evaluated, and are not intended to limit the scope of what theinventors regard as their invention. Unless indicated otherwise, partsare by weight, temperature is in ° C.

To facilitate observation of the reaction mixture and to insure thepurity of the product polycarbonate, melt transesterification reactionswere carried out in a 1 Liter glass batch reactor equipped with a solidnickel helical agitator. The reactor bottom had a breakaway glass nipplefor removal of the product polycarbonate as a melt. To remove any sodiumfrom the interior glass surfaces of the reactor, the reactor was soakedin 3N HCl for at least 12 hours, followed by soaking in 18 Mohm waterfor at least 12 hours. The reactor was then dried in an oven overnightand stored covered until use. The temperature of the reactor wasmaintained using a fluidised sand bath with a PID controller. Thetemperature was measured near the reactor and sand bath interface. Thepressure over the reactor was controlled by a nitrogen bleed into thevacuum pump downstream of the distillate collection flasks and measuredat higher pressures (760 mmHg-40 mmHg) with a mercury barometer and atlower pressures (40 mmHg-1 mmHg) with an Edwards pirani gauge.

The reactor was charged with solid bisphenol-A (General ElectricPlastics Japan Ltd., 0.6570 mol) and solid diphenyl carbonate (GeneralElectric Plastics Japan Ltd., 0.7096 mol) prior to assembly. The reactorwas then assembled, sealed, and the atmosphere was exchanged withnitrogen three times. With the final nitrogen exchange, the reactor wasbrought to near atmospheric pressure and submerged into the fluidisedbath that was at 180° C. After five minutes, agitation was begun at 250rpm. After an additional ten minutes the reactants were fully melted andthe mixture was assumed to be homogeneous. Tetramethylammonium hydroxide(TMAH) (Sachem, 1.32×10⁻⁴ mole) and the azonaphthalene sulfonatecatalyst (1-5×10⁻⁶ moles catalyst per mole bisphenol A) were added tothe mixture as solutions in deionized (18 Mohm) water. After catalystaddition, timing was begun and the temperature was ramped to 210° C. infive minutes. Once at temperature, the pressure was reduced to 180 mmHgand phenol distillate was immediately observed. After 25 minutes thepressure was again reduced to 100 mmHg and maintained for 45 minutes.The temperature was then ramped to 240° C. in five minutes and thepressure was lowered to 15 mmHg. These conditions were maintained for 45minutes. The temperature was then ramped to 270° C. in five minutes andthe pressure was lowered to 2 mmHg. These conditions were maintained for10 minutes. The temperature was then ramped to the final finishingtemperature in five minutes and the pressure was reduced to 1.1 mmHg.The finishing temperature was 310° C. After 30 minutes the reactor wasremoved from the sand bath and the product polymer melt was poured intoliquid nitrogen to quench the reaction.

Number average molecular weight (M_(n)) was obtained by gel permeationchromatography (GPC) analysis of the product polycarbonate. Apolycarbonate molecular weight standard of known molecular weight wasused to construct a calibration curve against which productpolycarbonate molecular weights could be determined. The temperature ofthe columns was 25° C. and the mobile phase was chloroform.

Fries content (ppm) was determined by KOH mediated hydrolysis of theproduct polycarbonate. The amount of Fries product for each of the meltpolycarbonates listed in Table 1 was determined as follows. First, 0.50grams of polycarbonate was dissolved in 4.0 ml of THF (containingp-terphenyl as internal standard). Next, 3.0 ml of 18% KOH in methanolwas added to this solution. The resulting mixture was stirred for twohours at this temperature. Next, 1.0 ml of acetic acid was added, andthe mixture was stirred for 5 minutes. Potassium acetate was allowed tocrystalize over 1 hour. The solid was filtered off and the resultingfiltrate was analyzed by liquid chromoatograph using p-terphenyl as theinternal standard.

Data are gathered in Table 1 which demonstrate the superiority of thecatalysts used according to the method of the present invention relativeto conventional catalysts. Conventional catalyst performance wasillustrated using a transesterification catalyst comprising sodiumhydroxide (CE-1) and sodium tosylate (CE-2). In Comparative Examples 1and 2 (CE-1 and CE-2) and in Examples 1-3 the catalyst was used in anamount corresponding to about 5×10⁻⁶ moles catalyst per mole bisphenolA, and the co-catalyst, TMAH, was present in an amount corresponding toabout 2.0×10⁻⁴ mole TMAH per mole bisphenol A. The product polycarbonatewas in all instances bisphenol A polycarbonate. In Table 1 the columnheading “Structure” indicates the structure of the principal catalystemployed. “Mn” denotes number average molecular weight in daltons of theproduct polycarbonate. The column heading “Fries” indicates the amountof Fries rearrangement product present in the product polycarbonate.“Fries” values are given in parts per million (ppm).

TABLE 1 Example Catalyst Structure M_(n) Fries Principal CatalystAmount: 5 × 10⁻⁶ moles per mole BPA CE-1 Sodium Hydroxide NaOH 8800 3000CE-2 Sodium Tosylate NaOTs 5938 240 Example 1 6,6′[(3,3′-dimethoxy[1,1′-III 7776 764 biphenyl]-4,4′- diyl)bis(azo)]bis[4-amino-5- hydroxy-1,3-naphthalenedisulfonic acid] tetrasodium salt Example 22,7-bis(naphthalene-1- IV 7097 256 ylazo)-naphthalene-1,8-dioltetrasulfonic acid tetrasodium salt Example 3 Beryllon H V 7632 286

The results in Table 1 clearly illustrate the effectiveness of theazonaphthalene sulfonates as melt polymerization catalysts as comparedto sodium hydroxide or sodium tosylate. In the case of sodium hydroxide(CE-1) the achievement of relatively high molecular weight (M_(n) atleast about 8800 daltons) results in the generation of a substantialamount (about 3000 ppm) of undesired Fries rearrangement product. Thecatalysts of the present invention provide product polycarbonates ofmoderately high molecular weight (Mn) with substantially reduced levelsof Fries rearrangement product relative to that produced when sodiumhydroxide is employed as the principal catalyst. Sodium tosylate (CE-2)is a much less effective polymerization catalyst (product polycarbonateM_(n)<7000 daltons) than the azonaphthalene sulfonates of the presentinvention.

This invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

What is claimed is:
 1. A method for the preparation of polycarbonatesaid method comprising contacting under melt polymerization conditionsat least one diaryl carbonate with at least one dihydroxy aromaticcompound in the presence of a transesterification catalyst to afford apolycarbonate, said transesterification catalyst comprising at least oneazonaphthalene sulfonate catalyst and at least one co-catalyst.
 2. Amethod of claim 1 wherein said azonaphthalene sulfonate catalyst hasstructure I

wherein Ar₁ is a C₄-C₆₀ aromatic radical having a valence of at leastone, said aromatic radical being optionally substituted by one or morehydroxy groups, amino groups, C₁-C₁₀ alkylarino groups, C₂-C₂₀dialkylamino groups, C₁-C₂₀ aliphatic radicals, C₄-C₂₀ cycloaliphaticradicals, C₄-C₁₀ aromatic radicals, C₁-C₁₀ alkoxy groups, halogen atoms,and alkali metal sulfonate groups; M is independently at each occurrencea lithium, sodium, potassium, or cesium ion; n and m are integersindependently having values of from 0 to 2 wherein the sum of n and m isalways greater than or equal to 1; R₁ is independently at eachoccurrence a hydroxy group, amino group, C₁-C₁₀ alkylamino group, C₂-C₂₀dialkylamino group, C₁-C₂₀ aliphatic radical, C₄-C₂₀ cycloaliphaticradical, C₄-C₁₀ aromatic radical, C₁-C₁₀ alkoxy group, halogen atom,nitro group, or a cyano group; q is an integer having a value of from 0to 3; p is an integer having a value of from 0-4; and r is an integerhaving a value of from 1-4.
 3. A method according to claim 2, whereinsaid catalyst is an azonaphthalene sulfonate catalyst having structureIII;

structure IV;

structure V; or

is a mixture of at least two of the azonaphthalene sulfonates III, IVand V.
 4. A method according to claim 1 wherein said dihydroxy aromaticcompound is a bisphenol having structure VI

wherein R² is independently at each occurrence a halogen atom, nitrogroup, cyano group, C₁-C₂₀ alkyl group, C₄-C₂₀ cycloalkyl group, orC₆-C₂₀ aryl group; b and c are independently integers 0-3; and W is abond, an oxygen atom, a sulfur atom, a SO₂ group, a C₁-C₂₀ aliphaticradical, a C₆-C₂₀ aromatic radical, a C₆-C₂₀ cycloaliphatic radical orthe group

wherein R³ and R⁴ are independently a hydrogen atom, C₁-C₂₀ alkyl group,C₄-C₂₀ cycloalkyl group, or C₄-C₂₀ aryl group; or R³ and R⁴ togetherform a C₄-C₂₀ cycloaliphatic ring which is optionally substituted by oneor more C₁-C₂₀ alkyl, C₆-C₂₀ aryl, C₅-C₂₁ aralkyl, C₅-C₂₀ cycloalkylgroups or a combination thereof.
 5. A method according to claim 4wherein said bisphenol is selected from the group consisting ofbisphenol A; 2,2-bis(4-hydroxy-3-methylphenyl)propane;2,2-bis(3-chloro-4-hydroxyphenyl)propane;2,2-bis(3-bromo-4-hydroxyphenyl)propane;2,2-bis(4-hydroxy-3-isopropylphenyl)propane;1,1-bis(4-hydroxyphenyl)cyclohexane;1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane; and1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.
 6. A methodaccording to claim 1 wherein said diaryl carbonate has structure VII

wherein R⁵ is independently at each occurrence a halogen atom, nitrogroup, cyano group, C₁-C₂₀ alkyl group, C₁-C₂₀ alkoxy carbonyl group,C₄-C₂₀ cycloalkyl group, or C₆-C₂₀ aryl group; and t and v areindependently integers 0-5.
 7. A method according to claim 6 whereinsaid diaryl carbonate is selected from the group consisting of diphenylcarbonate, bis(4-methylphenyl) carbonate, bis(4-chlorophenyl) carbonate,bis(4-fluorophenyl) carbonate, bis(2-chlorophenyl) carbonate,bis(2,4-difluorophenyl) carbonate, bis(4-nitrophenyl) carbonate,bis(2-nitrophenyl) carbonate, and bis(methyl salicyl) carbonate.
 8. Amethod according to claim 1 wherein said contacting at least one diarylcarbonate with at least one dihydroxy aromatic compound in the presenceof a transesterification catalyst comprising at least one azonaphthalenesulfonate catalyst and at least one co-catalyst under meltpolymerization conditions is carried out in the presence of one or morebranching agents.
 9. A method according to claim 8 wherein saidbranching agent is 1,1,1-tris(4-hydroxyphenyl)ethane.
 10. A methodaccording to claim 1 wherein said contacting at least one diarylcarbonate with at least one dihydroxy aromatic compound in the presenceof a transesterification catalyst comprising at least one azonaphthalenesulfonate catalyst and at least one co-catalyst under meltpolymerization conditions is carried out in the presence of at least oneendcapping agent.
 11. A method according to claim 10 wherein saidendcapping agent is a hydroxy aromatic compound.
 12. A method accordingto claim 11 wherein said hydroxy aromatic compound is selected from thegroup consisting of phenol, p-tert-butylphenol, p-cumylphenol, andcardanol.
 13. A method according to claim 1 wherein said azonaphthalenesulfonate catalyst is employed in an amount corresponding to between1×10⁻⁸ and 2.5×10⁻⁴ moles azonaphthalene sulfonate catalyst per moledihydroxy aromatic compound.
 14. A method according to claim 1 whereinsaid co-catalyst is selected from the group consisting of quaternaryammonium compounds, quaternary phosphonium compounds, and mixturesthereof.
 15. A method according to claim 14 wherein said quaternaryammonium compounds are selected from the group consisting of tetramethylammonium hydroxide and tetrabutylammonium hydroxide, and said quaternaryphosphonium compounds are selected from the group consisting oftetrabutyl phosphonium acetate and tetrabutylphosphonium hydroxide. 16.A method according to claim 1 wherein said co-catalyst is employed in anamount corresponding to between about 1×10⁻² and about 1×10⁻⁶ moles ofco-catalyst per mole of dihydroxy aromatic compound.
 17. A method forthe preparation of bisphenol A polycarbonate said method comprisingcontacting at least one diaryl carbonate with bisphenol A in thepresence of a transesterification catalyst, at a temperature in a rangebetween about 180° C. and about 310° C. and a pressure in a rangebetween about 760 and about 1 torr to afford a product polycarbonate,said transesterification catalyst comprising at least one azonaphthalenesulfonate catalyst and at least one co-catalyst.
 18. A method of claim17 wherein said azonaphthalene sulfonate catalyst has structure I

wherein Ar₁ is a C₄-C₆₀ aromatic radical having a valence of at leastone, said aromatic radical being optionally substituted by one or morehydroxy groups, amino groups, C₁-C₁₀ alkylamino groups, C₂-C₂₀dialkylamino groups, C₁-C₂₀ aliphatic radicals, C₄-C₂₀ cycloaliphaticradicals, C₄-C₁₀ aromatic radicals, C₁-C₁₀ alkoxy groups, halogen atoms,and alkali metal sulfonate groups; M is independently at each occurrencea lithium, sodium, potassium, or cesium ion; n and m are integersindependently having values of from 0 to 2 wherein the sum of n and m isalways greater than or equal to 1; R₁ is independently at eachoccurrence a hydroxy group, amino group, C₁-C₁₀ alkylamino group, C₂-C₂₀dialkylanino group, C₁-C₂₀ aliphatic radical, C₄-C₂₀ cycloaliphaticradical, C₄-C₁₀ aromatic radical, C₁-C₁₀ alkoxy group, halogen atom,nitro group, or a cyano group; q is an integer having a value of from 0to 3; p is an integer having a value of from 0-4; and r is an integerhaving a value of from 1-4.
 19. A method according to claim 17 whereinsaid diaryl carbonate has structure VII

wherein R⁵ is independently at each occurrence a halogen atom, nitrogroup, cyano group, C₁-C₂₀ alkyl group, C₁-C₂₀ alkoxy carbonyl group,C₄-C₂₀ cycloalkyl group, or C₆-C₂₀ aryl group; and t and v areindependently integers 0-5.
 20. A method according to claim 19 whereinsaid diaryl carbonate is selected from the group consisting of diphenylcarbonate, bis(4-methylphenyl) carbonate, bis(4-chlorophenyl) carbonate,bis(4-fluorophenyl) carbonate, bis(2-chlorophenyl) carbonate,bis(2,4-difluorophenyl) carbonate, bis(4-nitrophenyl) carbonate,bis(2-nitrophenyl) carbonate, and bis(methyl salicyl) carbonate.
 21. Amethod according to claim 19 wherein said azonaphthalene sulfonatecatalyst is employed in an amount corresponding to between 1×10⁻⁸ and2.5×10⁻⁴ moles azonaphthalene sulfonate catalyst per mole bisphenol A.22. A method according to claim 19 wherein said co-catalyst is selectedfrom the group consisting of quaternary ammonium compounds, quaternaryphosphonium compounds, and mixtures thereof.
 23. A method according toclaim 22 wherein said quaternary ammonium compounds are selected fromthe group consisting of tetramethyl ammonium hydroxide and tetrabutylammonium hydroxide, and said quaternary phosphonium compounds areselected from the group consisting of tetrabutyl phosphonium acetate andtetrabutylphosphonium hydroxide.
 24. A method for the preparation ofbisphenol A polycarbonate, said method comprising contacting bisphenol Awith diphenyl carbonate at a temperature in a range between about 180°C. and about 310° C. and a pressure in a range between about 760 torrand about 1 torr in the presence of at least one azonaphthalenesulfonate and tetrabutylphosphonium acetate, said diphenyl carbonatebeing present in an amount corresponding to between about 0.9 and about1.2 moles diphenyl carbonate per mole of bisphenol A, saidazonaphthalene sulfonate being present in an amount corresponding tobetween about 1×10⁻⁸ and about 2.5×10⁻⁴ moles azonaphtalaene-sulfonateper mole bisphenol A employed, said tetrabutylphosphonium acetate beingpresent in an amount corresponding to between about 1×10⁻⁶ and about1×10⁻² moles tetrabutylphosphonium acetate per mole bisphenol Aemployed.